WO2019138893A1 - Moisture-curable hot-melt adhesive and bonded article - Google Patents

Moisture-curable hot-melt adhesive and bonded article Download PDF

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WO2019138893A1
WO2019138893A1 PCT/JP2018/047915 JP2018047915W WO2019138893A1 WO 2019138893 A1 WO2019138893 A1 WO 2019138893A1 JP 2018047915 W JP2018047915 W JP 2018047915W WO 2019138893 A1 WO2019138893 A1 WO 2019138893A1
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moisture
hot melt
melt adhesive
curable hot
adhesive
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PCT/JP2018/047915
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French (fr)
Japanese (ja)
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耕祐 横山
優香 山下
剛 早坂
崇司 川守
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日立化成株式会社
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Priority to JP2019564633A priority Critical patent/JPWO2019138893A1/en
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
    • C09J175/04—Polyurethanes
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J5/00—Adhesive processes in general; Adhesive processes not provided for elsewhere, e.g. relating to primers
    • C09J5/06—Adhesive processes in general; Adhesive processes not provided for elsewhere, e.g. relating to primers involving heating of the applied adhesive

Definitions

  • the present invention relates to a moisture curable hot melt adhesive and an adhesive.
  • the hot melt adhesive is a non-solvent type adhesive, so the load on the environment and the human body is small and adhesion is possible for a short time, so it is an adhesive suitable for improving productivity.
  • Hot melt adhesives can be roughly classified into two, those having a thermoplastic resin as a main component and those having a reactive resin as a main component. In those having a reactive resin as a main component, a urethane prepolymer having an isocyanate group at the end is mainly used.
  • the reactive hot melt adhesive mainly composed of a urethane prepolymer develops a certain degree of adhesive strength in a short time due to cooling and solidification of the adhesive itself after application.
  • the terminal isocyanate group of the urethane prepolymer reacts with the moisture in the air or the moisture on the surface of the adherend to form a high molecular weight, and by causing crosslinking, a cured product is formed to develop heat resistance.
  • Reactive hot melt adhesives having such properties are called moisture-curable hot melt adhesives. Therefore, a moisture-curable hot melt adhesive containing a urethane prepolymer as a main component tends to exhibit good adhesive strength even when heated.
  • the present invention has been made in view of such circumstances, and it is a main object of the present invention to provide a moisture-curable hot melt adhesive which is excellent in stretchability and also excellent in adhesiveness even when applied to a cloth. Do.
  • One aspect of the present invention relates to a polymer chain comprising a structural unit derived from at least one selected from the group consisting of polybutadiene polyol and hydrogenated polybutadiene polyol and a structural unit derived from polyisocyanate, and an isocyanate group at the end of the polymer chain
  • a moisture-curable hot melt adhesive which comprises a urethane prepolymer having a tensile modulus of 10 MPa or less after curing.
  • the stretch recovery after curing of the moisture-curable hot melt adhesive may be 90% or more.
  • the polymerization chain may contain structural units derived from hydrogenated polybutadiene polyol.
  • Moisture curable hot melt adhesives may be used to bond a plurality of fabrics or papers together.
  • the target of lamination may be cloth and cloth, paper and paper, or cloth and paper.
  • the present invention further relates to a moisture-curable hot-melt adhesive used to bond together a plurality of cloths or papers of a composition containing the above-mentioned urethane prepolymer and having a tensile modulus of 10 MPa or less after curing.
  • the present invention may also be directed to applications for the manufacture of moisture curable hot melt adhesives used to bond multiple fabrics or papers together.
  • the present invention provides an adhesive comprising: a plurality of cloths or papers; and a cured product of the above-mentioned moisture-curable hot melt adhesive for bonding a plurality of cloths or papers to each other.
  • a moisture-curable hot melt adhesive which is excellent in stretchability and further excellent in adhesiveness even when applied to a cloth. Further, according to the present invention, there is provided an adhesive using such a moisture-curable hot melt adhesive.
  • FIG. 1 (a), (b), (c), and (d) is a schematic diagram which shows each process.
  • polyol means a compound having an average of more than 1 hydroxyl group in the molecule.
  • polyisocyanate means a compound having an average of more than one isocyanate group in the molecule.
  • the moisture-curable hot melt adhesive includes a polymerization chain including a structural unit derived from at least one selected from the group consisting of polybutadiene polyol and hydrogenated polybutadiene polyol, and a structural unit derived from polyisocyanate, and polymerization. It contains a urethane prepolymer having an isocyanate group at the end of the chain.
  • a moisture-curable hot melt adhesive can be made to have a high molecular weight by a chemical reaction and can exhibit adhesiveness and the like.
  • a urethane prepolymer having an isocyanate group at the end of the polymerization chain can react with moisture to cure (form a cured product), and thus the urethane prepolymer alone can function as a moisture-curable hot melt adhesive.
  • the moisture-curable hot melt adhesive may contain components other than the urethane prepolymer.
  • the urethane prepolymer has a polymer chain containing a structural unit derived from at least one selected from the group consisting of polybutadiene polyol and hydrogenated polybutadiene polyol and a polyisocyanate derived structure, and an isocyanate group at the end of the polymer chain Have.
  • the urethane prepolymer can be generally obtained by reacting polyisocyanate with at least one selected from the group consisting of polybutadiene polyol and hydrogenated polybutadiene polyol. That is, the urethane prepolymer may be a reactant of such a polyol and a polyisocyanate.
  • the polybutadiene polyol is a compound having a polymer chain derived from butadiene and hydroxyl groups at both ends of the polymer chain, etc.
  • the hydrogenated polybutadiene polyol is a hydrogenated product of polybutadiene polyol.
  • the polybutadiene polyol and the hydrogenated polybutadiene polyol may have an average of about 1.8 to 2.5 hydroxyl groups in the molecule.
  • Polybutadiene and a polymer chain derived from its hydrogenated substance can act as an elastomer, and having such a polymer chain makes it possible to impart adhesiveness and elasticity to the urethane prepolymer.
  • the polymerization chain of the urethane prepolymer preferably contains structural units derived from a hydrogenated polybutadiene polyol.
  • polybutadiene polyol and hydrogenated polybutadiene polyol commercially available products can be used as they are.
  • examples of commercially available products of hydrogenated polybutadiene polyol include GI-1000, GI-2000, GI-3000 (all trade names, manufactured by Nippon Tanka Co., Ltd.) and the like.
  • polybutadiene polyol for example, G-1000, G-2000, G-3000 (all are trade names, manufactured by Nippon Tanka Co., Ltd.), Poly bd R-15HT, Poly bd R-45 HT (all are goods) Names, manufactured by Idemitsu Kosan Co., Ltd., Krasol LBH-P3000 (trade name, manufactured by Clay Valley, Inc.), and the like. One of these may be used alone, or two or more may be used in combination.
  • the number average molecular weight (Mn) of the polybutadiene polyol and the hydrogenated polybutadiene polyol may be 500 to 100,000, 700 to 50,000, or 900 to 10,000, from the viewpoint of the balance of viscosity and adhesion.
  • the number average molecular weight (Mn) is a value measured by gel permeation chromatography (GPC) and converted into standard polystyrene.
  • a polybutadiene polyol and a hydrogenated polybutadiene polyol may be used in combination with a polyol capable of reacting with a polyisocyanate (hereinafter referred to as "other polyol").
  • other polyols include polyester polyols, polyether polyols, polyacrylate polyols, polycarbonate polyols, polysiloxane polyols, polyisoprene polyols, polyolefin polyols and the like.
  • the other polyols may be used alone or in combination of two or more.
  • the total content of the polybutadiene polyol and the hydrogenated polybutadiene polyol may be 30% by mass or more based on the total amount of the polyols (polybutadiene polyol and hydrogenated polybutadiene polyol, and other polyols).
  • the content of the polybutadiene polyol and the hydrogenated polybutadiene polyol may be 40% by mass, 50% by mass or more, 70% by mass or more, or 90% by mass or more, based on the total amount of the polyol.
  • the polyol may be composed only of polybutadiene polyol and hydrogenated polybutadiene polyol. As the content of the polybutadiene diol and the hydrogenated polybutadiene diol increases, the stretch recovery after curing of the moisture-curable hot melt adhesive tends to increase.
  • the content of the other polyol may be 0 to 70% by mass, 0 to 60% by mass, 0 to 50% by mass, 0 to 30% by mass, or 0 to 10% by mass, based on the total amount of the polyol.
  • the polyisocyanate is not particularly limited as long as it is a polyisocyanate having two or more isocyanate groups.
  • the polyisocyanate is preferably a diisocyanate from the viewpoint of handleability at the time of reaction.
  • diisocyanates examples include aromatic polyisocyanates such as diphenylmethane diisocyanate, dimethyl diphenylmethane diisocyanate, tolylene diisocyanate, xylylene diisocyanate, p-phenylene diisocyanate, aliphatic polyisocyanates such as hexamethylene diisocyanate, dicyclohexylmethane diisocyanate, iso Alicyclic polyisocyanates such as folone diisocyanate may, for example, be mentioned.
  • the polyisocyanate may be used alone or in combination of two or more. Among these, the polyisocyanate preferably contains diphenylmethane diisocyanate.
  • the urethane prepolymer has an isocyanate group at the end of a polymer chain containing a structural unit derived from a polyol and a structural unit derived from a polyisocyanate.
  • the mixing ratio of polyisocyanate and polyol is: isocyanate group (NCO) equivalent of polyisocyanate / hydroxyl group equivalent (OH) of polyol ((NCO) equivalent / (OH) equivalent) It is preferable to adjust to 1.1 or more.
  • the (NCO) equivalent / (OH) equivalent may be 1.1 to 2.2 or 1.1 to 2.1.
  • the (NCO) equivalent / (OH) equivalent When the (NCO) equivalent / (OH) equivalent is 1.1 or more, the increase in the viscosity of the resulting urethane prepolymer can be suppressed, and the workability tends to be easily improved. When the (NCO) equivalent / (OH) equivalent is 2.2 or less, foaming during the moisture curing reaction of the urethane prepolymer is less likely to occur, and the decrease in adhesion tends to be suppressed.
  • the weight average molecular weight (Mw) of the urethane prepolymer may be 10000 or more, 12000 or more, or 14000 or more, and may be 1000000 or less, 500000 or less, 300000 or less, 200,000 or less, or 150,000 or less.
  • the weight average molecular weight (Mw) of the urethane prepolymer may be 10,000 to 1,000,000, 50,000 to 500,000, or 100,000 to 300,000.
  • the weight average molecular weight of the urethane prepolymer tends to be higher as the (NCO) equivalent / (OH) equivalent is closer to 1.
  • the higher the weight average molecular weight of the urethane prepolymer the higher the viscosity tends to be.
  • the moisture-curable hot melt adhesive may further contain a thermoplastic polymer from the viewpoint of enhancing the rubber elasticity and imparting stronger adhesion.
  • a thermoplastic polymer examples include polyurethane, ethylene-based copolymer, propylene-based copolymer, vinyl chloride-based copolymer, acrylic copolymer, and styrene-conjugated diene block copolymer.
  • the content of the thermoplastic polymer may be 10 to 50% by mass based on the total amount of the moisture curable hot melt adhesive.
  • the moisture-curable hot melt adhesive may further contain a tackifier from the viewpoint of imparting stronger adhesiveness.
  • a tackifier for example, rosin resin, rosin ester resin, hydrogenated rosin ester resin, terpene resin, terpene phenol resin, hydrogenated terpene resin, petroleum resin, hydrogenated petroleum resin, coumarone resin, ketone resin, styrene resin, Modified styrene resin, xylene resin, epoxy resin and the like can be mentioned.
  • the content of the tackifier may be 10 to 50% by mass based on the total amount of the moisture-curable hot melt adhesive.
  • the total content of the thermoplastic polymer and the tackifier may be 10 to 50% by mass based on the total amount of the moisture-curable hot melt adhesive.
  • the moisture curable hot melt adhesive may further contain a catalyst.
  • the catalyst include dibutyltin dilaurate, dibutyltin octoate, dimethylcyclohexylamine, dimethylbenzylamine, trioctylamine, dimorpholinodiethyl ether and the like.
  • the content of the catalyst may be 0.001 to 0.5% by mass based on the total amount of the moisture curing type hot melt adhesive.
  • the moisture-curable hot melt adhesive may further contain other components, as required.
  • Other components include, for example, antioxidants, pigments, UV absorbers, surfactants, flame retardants, fillers, photochromic agents, thermal color development inhibitors, fragrances, imaging agents, thermal crosslinking agents, and the like.
  • the content of the other components may be 0.001 to 10% by mass based on the total amount of the moisture-curable hot melt adhesive.
  • the viscosity at 120 ° C. of the moisture-curable hot melt adhesive is 0.01 Pa ⁇ s or more, 0.05 Pa ⁇ s or more, 0.1 Pa ⁇ s or more, or 0. It may be 5 Pa ⁇ s or more, 100 Pa ⁇ s or less, 80 Pa ⁇ s or less, 60 Pa ⁇ s or less, or 50 Pa ⁇ s or less.
  • the viscosity at 120 ° C. is in the above range, the workability at the time of coating with a dispenser or the like is improved.
  • the moisture-curable hot melt adhesive is, for example, cured for 1 day at 23 ° C. because the terminal isocyanate group of the urethane prepolymer contained in the adhesive reacts with the moisture in the air or the moisture on the surface of the adherend. It is possible to cure (make it possible to obtain a cured product of a moisture-curable hot melt adhesive).
  • the adhesive strength (the initial adhesive strength of the moisture-curable hot melt adhesive) measured before the adhesive is cured after pressure-adhering the adherends to each other using the moisture-curable hot melt adhesive is 0.013 N. / Mm (0.1 N / 8 mm) or more, 0.038 N / mm (0.3 N / 8 mm) or more, 0.063 N / mm (0.5 N / 8 mm) or more, 0.125 N / mm (1.0 N / 8 mm) Or higher, or 0.188 N / mm (1.5 N / 8 mm) or higher.
  • the upper limit of the adhesive strength of the cured product is not particularly limited, but may be 1.5 N / mm (12 N / 8 mm) or less.
  • the adhesive strength of an initial stage means the value measured by the method as described in an Example. That is, in the pressure-bonded body obtained by pressure-adhering the adherends at 120 ° C. using a moisture curing type hot melt adhesive, the initial adhesive strength is moisture curing of the pressure-bonded body after 5 minutes from the time of pressure bonding.
  • the adhesive strength of the mold hot melt adhesive is meant.
  • the adhesive strength (adhesive strength after curing of the moisture-curable hot melt adhesive) measured after the adhesive is cured after the adherends are pressure-bonded to each other using the moisture-curable hot melt adhesive is 0.063 N / Mm (0.5 N / 8 mm) or more, 0.125 N / mm (1.0 N / 8 mm) or more, 0.188 N / mm (1.5 N / 8 mm) or more, 0.375 N / mm (3 N / 8 mm) or more , 0.625 N / mm (5 N / 8 mm) or more, or 0.875 N / mm (7 N / 8 mm) or more.
  • the upper limit of the adhesive strength after curing is not particularly limited, but may be 2.5 N / mm (20 N / 8 mm) or less.
  • the adhesive strength after curing means a value measured by the method described in the examples. That is, the adhesive strength after curing is that a pressure-bonded body obtained by pressure-adhering adherends at 120 ° C. using a moisture-curable hot melt adhesive is cured for 1 day in a thermostatic chamber at 23 ° C. and 50% RH. And the adhesive strength after curing of the moisture-curable hot melt adhesive of the resulting bonded body.
  • the tensile modulus after curing of the moisture-curable hot melt adhesive (the tensile modulus of the cured product of the moisture-curable hot melt adhesive) is 10 MPa or less.
  • the tensile modulus after curing of the moisture-curable hot melt adhesive may be 0.01 MPa or more, 0.05 MPa or more, or 0.1 MPa or more from the viewpoint of flexibility, 8 MPa or less, 6 MPa or less, or 4 MPa It may be the following.
  • the sense of incongruity at the time of wearing can be lessened because tensile elastic modulus is in the above-mentioned range.
  • the tensile modulus after curing means a value measured by the method described in the examples. That is, the tensile elastic modulus after curing means the tensile elastic modulus of a cured product obtained by curing a moisture curing type hot melt adhesive by curing for 1 day in a constant temperature bath at 23 ° C. and 50% RH.
  • the stretch recovery after curing of the moisture-curable hot melt adhesive may be 90% or more, 93% or more, or 95% or more.
  • the expansion-contraction recovery factor after hardening means the value measured by the method as described in an Example. That is, the stretch recovery rate after curing means the stretch recovery rate of a cured product obtained by curing a moisture curing type hot melt adhesive by curing it in a constant temperature bath at 23 ° C. and 50% RH for 1 day.
  • the moisture-curable hot melt adhesive can be used, for example, by melting it at 60 to 130 ° C. and then applying it to an adherend.
  • the coating method is not particularly limited, and examples thereof include methods using a coating apparatus such as a die coater, a roll coater, or a spray.
  • a dispenser is suitable for application to narrow parts such as small parts.
  • the adherend is not particularly limited, and may be, for example, cloth or paper.
  • the moisture-curable hot melt adhesive according to the present embodiment can be suitably used to bond a plurality of cloths or papers together.
  • the target of bonding may be cloth and cloth, paper and paper, or cloth and paper.
  • the moisture-curable hot melt adhesive may be used in the form of a film.
  • the moisture curable hot melt adhesive film can be formed, for example, by applying a moisture curable hot melt adhesive on a support film such as a PET film.
  • the thickness of the moisture curable hot melt adhesive film may be 10 ⁇ m or more, 20 ⁇ m or more, or 30 ⁇ m or more, and may be 300 ⁇ m or less, 250 ⁇ m or less, or 200 ⁇ m or less.
  • the moisture-curable hot melt adhesive is obtained, for example, by reacting a polyol containing at least one member selected from the group consisting of polybutadiene polyol and hydrogenated polybutadiene polyol with a polyisocyanate to obtain a urethane prepolymer, if necessary And mixing the urethane prepolymer with other optional components.
  • the moisture curing type hot melt adhesive according to the present embodiment can be suitably used for apparel products such as clothes, supporters, bags, wallets, interiors, various covers, cases, wearable devices, and the like.
  • An adhesive according to one embodiment comprises a plurality of cloths or papers, and a cured product of the above-mentioned moisture-curable hot melt adhesive for bonding a plurality of cloths or papers to one another.
  • the adhesive body according to the present embodiment can be used as a non-sewn garment or the like, for example, when the adherend is an adhesive body of cloth and cloth.
  • the adhesive may be, for example, a cloth or paper coated with the above-mentioned moisture-curable hot melt adhesive to form an adhesive layer, and a cloth or paper placed on the adhesive layer and crimped to form an adhesive precursor. And curing the resulting adhesive precursor in air (eg, curing for 1 day at 23 ° C.) and curing the adhesive layer (moisture-curable hot melt adhesive). It can be manufactured by the method. In the step of obtaining an adhesive precursor, for example, a pressure roll or the like can be used.
  • FIG. 1 is a schematic diagram which shows an example of the process of producing the adhesive body which concerns on one Embodiment
  • FIG. 1 (a), (b), (c) and (d) is a schematic diagram which shows each process. It is. With reference to FIG. 1, the manufacturing process of the bonded body using elastic fabric as cloth is demonstrated.
  • the stretchable fabric 1 is installed along the jig 10 (see (a) of FIG. 1).
  • the moisture-curable hot melt adhesive according to the present embodiment is applied to a predetermined portion of the stretchable fabric 1 to form an adhesive layer 4 (see (b) in FIG. 1).
  • the material and shape of the jig 10 are not particularly limited, and can be appropriately selected according to the purpose.
  • the application of the adhesive may be performed, for example, using a dispenser.
  • the stretchable fabric 2 is placed on the adhesive layer 4 and the stretchable fabric 1 and the stretchable fabric 2 are interposed between the adhesive layer 4 while applying pressure from above the stretchable fabric 2 by a roll or the like. It bonds together and obtains an adhesion body precursor (refer (c) and (d) of FIG. 1).
  • the adhesive layer 4 is moisture-cured to obtain an adhesive of the stretchable fabric.
  • the adhesive previously formed on the releasable substrate may be transferred onto the stretchable fabric 1 to form the adhesive layer 4.
  • an adhesive may be provided on the stretchable fabric 2 to be bonded to the stretchable fabric 1.
  • the resulting urethane prepolymer is a structural unit derived from at least one selected from the group consisting of polybutadiene polyol and hydrogenated polybutadiene polyol. It is also presumed that the polymer has a polymer chain containing a structural unit derived from a polyisocyanate and an isocyanate group at the end of the polymer chain.
  • the obtained urethane prepolymer was used as it was as a moisture-curable hot melt adhesive.
  • Hydrogenated polybutadiene polyol A-1 Nippon Soda Co., Ltd., trade name: GI-3000, number average molecular weight: 3100
  • Hydrogenated polybutadiene polyol A-2 Nippon Soda Co., Ltd., trade name: GI-1000, number average molecular weight: 1,500
  • Polybutadiene polyol B-1 Idemitsu Kosan Co., Ltd., trade name: Poly bd TM R-45HT, a number average molecular weight: 2800
  • Polybutadiene polyol B-2 manufactured by Clay Valley, trade name: Krasol (registered trademark) LBH-P 3000, number average molecular weight: 3200 Diphenylmethane diisocyanate: manufactured by Nippon Polyurethane Industry Co., Ltd., trade name: Millionate MT
  • ⁇ Weight average molecular weight of urethane prepolymer> The weight average molecular weight of the obtained urethane prepolymer was measured by gel permeation chromatography (GPC) and determined by conversion using a standard polystyrene calibration curve.
  • GPC gel permeation chromatography
  • HLC-8220GPC manufactured by Tosoh Corp.
  • tetrahydrofuran was used as an eluent. The results are shown in Table 1.
  • the moisture-curable hot melt adhesive of Examples 1-6 was melted at 120 ° C., applied onto a PET film, and applied to a thickness of 80 ⁇ m using a bar coater to form an adhesive layer.
  • the formed adhesive layer was cured by curing in a thermostat bath at 23 ° C. and 50% RH for 1 day to obtain a cured product of the adhesive layer.
  • the cured product of the adhesive layer obtained was punched into a size of 5 mm ⁇ 50 mm, and the PET film was peeled off to obtain a measurement sample.
  • Tensile modulus and stretch recovery rate are measured using a tensile tester (EZ-Test EZ-SX, manufactured by Shimadzu Corporation) at a temperature of 25 ° C, a tensile speed of 100 mm / min, and a distance between chucks of 30 mm. It measured by.
  • the tensile modulus after curing was determined from the slope of the stress-strain curve at the initial stage of tension.
  • ⁇ Adhesive strength of moisture curing type hot melt adhesive> The moisture-curable hot melt adhesive of Examples 1 to 6 is melted at 120 ° C. and applied onto a stretchable fabric (Spandex, Lycra (registered trademark) manufactured by Toray Oplontex Co., Ltd.), and 80 ⁇ m by a bar coater. An adhesive layer was formed by coating to a thickness of The same stretchable fabric was placed on the formed adhesive layer, and a crimped body was obtained by crimping at 120 ° C.
  • a stretchable fabric (Spandex, Lycra (registered trademark) manufactured by Toray Oplontex Co., Ltd.)
  • An adhesive layer was formed by coating to a thickness of The same stretchable fabric was placed on the formed adhesive layer, and a crimped body was obtained by crimping at 120 ° C.
  • the adhesive strength of the pressure-bonded body after 5 minutes from the time of pressure bonding was measured using a force gauge (manufactured by Imada Co., Ltd., DS250N) to determine the initial adhesive strength of the moisture-curable hot melt adhesive.
  • a force gauge manufactured by Imada Co., Ltd., DS250N
  • the above-mentioned pressure-bonded body was aged in a thermostat bath at 23 ° C. and 50% RH for 1 day, and the adhesive layer was cured to prepare an adhesive body.
  • the adhesive strength of the adhesive is measured by a T-peel strength test under the conditions of a measurement temperature of 25 ° C.
  • the moisture-curable hot melt adhesives of Examples 1 to 6 had a high stretch recovery rate and were excellent in adhesive strength even when applied to a cloth. From these results, it was confirmed that the moisture-curable hot melt adhesive of the present invention is excellent in stretchability and also excellent in adhesiveness even when applied to a cloth.

Abstract

Disclosed is a moisture-curable hot-melt adhesive containing a urethane prepolymer having a polymer chain containing structural units derived from at least one selected from the group consisting of polybutadiene polyols and hydrogenated polybutadiene polyols and structural units derived from a polyisocyanate and having isocyanate groups at the ends of the polymer chain, the moisture-curable hot-melt adhesive having a tensile modulus of 10 MPa or lower after curing.

Description

湿気硬化型ホットメルト接着剤及び接着体Moisture curable hot melt adhesive and adhesive
　本発明は、湿気硬化型ホットメルト接着剤及び接着体に関する。 The present invention relates to a moisture curable hot melt adhesive and an adhesive.
　ホットメルト接着剤は、無溶剤型の接着剤であるため、環境及び人体への負荷が少なく、短時間接着が可能であるため、生産性向上に適した接着剤である。ホットメルト接着剤は、熱可塑性樹脂を主成分としたもの及び反応性樹脂を主成分としたものの２つに大別できる。反応性樹脂を主成分としたものでは、主にイソシアネート基を末端に有するウレタンプレポリマーが利用されている。ウレタンプレポリマーを主成分とする反応性ホットメルト接着剤は、塗布後、接着剤自体の冷却固化により、短時間で、ある程度の接着強度を発現する。その後、ウレタンプレポリマーの末端イソシアネート基が空気中の水分又は被着体表面の水分と反応することにより高分子量化し、架橋を生じることにより硬化物を形成して耐熱性を発現する。このような性質を有する反応性ホットメルト接着剤は、湿気硬化型ホットメルト接着剤と呼ばれる。そのため、ウレタンプレポリマーを主成分とする湿気硬化型ホットメルト接着剤は、加熱時でも良好な接着強度を示す傾向にある。 The hot melt adhesive is a non-solvent type adhesive, so the load on the environment and the human body is small and adhesion is possible for a short time, so it is an adhesive suitable for improving productivity. Hot melt adhesives can be roughly classified into two, those having a thermoplastic resin as a main component and those having a reactive resin as a main component. In those having a reactive resin as a main component, a urethane prepolymer having an isocyanate group at the end is mainly used. The reactive hot melt adhesive mainly composed of a urethane prepolymer develops a certain degree of adhesive strength in a short time due to cooling and solidification of the adhesive itself after application. Thereafter, the terminal isocyanate group of the urethane prepolymer reacts with the moisture in the air or the moisture on the surface of the adherend to form a high molecular weight, and by causing crosslinking, a cured product is formed to develop heat resistance. Reactive hot melt adhesives having such properties are called moisture-curable hot melt adhesives. Therefore, a moisture-curable hot melt adhesive containing a urethane prepolymer as a main component tends to exhibit good adhesive strength even when heated.
　近年、湿気硬化型ホットメルト接着剤は、衣類、おむつ等の素材である布、紙等にも使用されつつある。また、ウェアラブル製品が次々と開発されており、接着性に加えて、高い伸縮性を有する接着剤に対する需要が高まっている。このような用途に用いられる湿気硬化型ホットメルト接着剤としては、例えば、特許文献１、２に記載の接着剤が開示されている。しかし、接着性と伸縮性とを高いレベルで両立しているものは開発されておらず、未だ改善の余地がある。 In recent years, moisture curing type hot melt adhesives are being used for cloth, paper, etc. which are materials of clothes, diapers and the like. In addition, wearable products are being developed one after another, and in addition to adhesiveness, the demand for an adhesive having high stretchability is increasing. As moisture-curable hot melt adhesives used for such applications, for example, the adhesives described in Patent Documents 1 and 2 are disclosed. However, a combination of adhesiveness and stretchability at a high level has not been developed, and there is still room for improvement.
特開平１０－０８８０９７号公報Japanese Patent Application Laid-Open No. 10-088097 特開２０１７－０２００３７号公報Unexamined-Japanese-Patent No. 2017-020037
　本発明は、このような実情に鑑みてなされたものであり、伸縮性に優れ、さらに布に適用した場合においても接着性に優れる湿気硬化型ホットメルト接着剤を提供することを主な目的とする。 The present invention has been made in view of such circumstances, and it is a main object of the present invention to provide a moisture-curable hot melt adhesive which is excellent in stretchability and also excellent in adhesiveness even when applied to a cloth. Do.
　本発明の一側面は、ポリブタジエンポリオール及び水素化ポリブタジエンポリオールからなる群より選ばれる少なくとも１種に由来する構造単位並びにポリイソシアネートに由来する構造単位を含む重合鎖と、重合鎖の末端にイソシアネート基と、を有するウレタンプレポリマーを含有し、硬化後の引張弾性率が１０ＭＰａ以下である、湿気硬化型ホットメルト接着剤を提供する。 One aspect of the present invention relates to a polymer chain comprising a structural unit derived from at least one selected from the group consisting of polybutadiene polyol and hydrogenated polybutadiene polyol and a structural unit derived from polyisocyanate, and an isocyanate group at the end of the polymer chain There is provided a moisture-curable hot melt adhesive which comprises a urethane prepolymer having a tensile modulus of 10 MPa or less after curing.
　湿気硬化型ホットメルト接着剤の硬化後の伸縮回復率は９０％以上であってよい。重合鎖は水素化ポリブタジエンポリオールに由来する構造単位を含んでいてよい。 The stretch recovery after curing of the moisture-curable hot melt adhesive may be 90% or more. The polymerization chain may contain structural units derived from hydrogenated polybutadiene polyol.
　湿気硬化型ホットメルト接着剤は、複数の布又は紙を互いに貼り合わせるために用いられるものであってよい。ここで、貼り合わせの対象は、布と布、紙と紙、又は布と紙であってよい。 Moisture curable hot melt adhesives may be used to bond a plurality of fabrics or papers together. Here, the target of lamination may be cloth and cloth, paper and paper, or cloth and paper.
　本発明は、さらに上述のウレタンプレポリマーを含有し、硬化後の引張弾性率が１０ＭＰａ以下である組成物の、複数の布若しくは紙を互いに貼り合わせるために用いられる湿気硬化型ホットメルト接着剤としての応用又は複数の布若しくは紙を互いに貼り合わせるために用いられる湿気硬化型ホットメルト接着剤の製造のための応用に関してもよい。 The present invention further relates to a moisture-curable hot-melt adhesive used to bond together a plurality of cloths or papers of a composition containing the above-mentioned urethane prepolymer and having a tensile modulus of 10 MPa or less after curing. The present invention may also be directed to applications for the manufacture of moisture curable hot melt adhesives used to bond multiple fabrics or papers together.
　別の側面において、本発明は、複数の布又は紙と、複数の布又は紙を互いに接着する上述の湿気硬化型ホットメルト接着剤の硬化物と、を備える、接着体を提供する。 In another aspect, the present invention provides an adhesive comprising: a plurality of cloths or papers; and a cured product of the above-mentioned moisture-curable hot melt adhesive for bonding a plurality of cloths or papers to each other.
　本発明によれば、伸縮性に優れ、さらに布に適用した場合においても接着性に優れる湿気硬化型ホットメルト接着剤が提供される。また、本発明によれば、このような湿気硬化型ホットメルト接着剤を用いた接着体が提供される。 According to the present invention, there is provided a moisture-curable hot melt adhesive which is excellent in stretchability and further excellent in adhesiveness even when applied to a cloth. Further, according to the present invention, there is provided an adhesive using such a moisture-curable hot melt adhesive.
一実施形態に係る接着体を作製する工程の一例を示す模式図であり、図１（ａ）、（ｂ）、（ｃ）、及び（ｄ）は、各工程を示す模式図である。It is a schematic diagram which shows an example of the process of producing the adherend which concerns on one Embodiment, and FIG. 1 (a), (b), (c), and (d) is a schematic diagram which shows each process.
　以下、本発明を実施するための形態について詳細に説明する。ただし、本発明は以下の実施形態に限定されるものではない。 Hereinafter, modes for carrying out the present invention will be described in detail. However, the present invention is not limited to the following embodiments.
　本明細書において、「ポリオール」は、分子内に平均１を超える水酸基を有する化合物を意味する。 As used herein, "polyol" means a compound having an average of more than 1 hydroxyl group in the molecule.
　本明細書において、「ポリイソシアネート」は、分子内に平均１を超えるイソシアネート基を有する化合物を意味する。 As used herein, "polyisocyanate" means a compound having an average of more than one isocyanate group in the molecule.
＜湿気硬化型ホットメルト接着剤＞
　一実施形態に係る湿気硬化型ホットメルト接着剤は、ポリブタジエンポリオール及び水素化ポリブタジエンポリオールからなる群より選ばれる少なくとも１種に由来する構造単位並びにポリイソシアネートに由来する構造単位を含む重合鎖と、重合鎖の末端にイソシアネート基と、を有するウレタンプレポリマーを含有する。一般に、湿気硬化型ホットメルト接着剤は、化学反応によって高分子量化し、接着性等を発現し得るものである。重合鎖の末端にイソシアネート基を有するウレタンプレポリマーは、湿気と反応して硬化する（硬化物を形成する）ことから、ウレタンプレポリマー単独で湿気硬化型ホットメルト接着剤として作用し得る。また、湿気硬化型ホットメルト接着剤は、ウレタンプレポリマー以外の成分を含有していてもよい。 Moisture-curable hot melt adhesive
The moisture-curable hot melt adhesive according to one embodiment includes a polymerization chain including a structural unit derived from at least one selected from the group consisting of polybutadiene polyol and hydrogenated polybutadiene polyol, and a structural unit derived from polyisocyanate, and polymerization. It contains a urethane prepolymer having an isocyanate group at the end of the chain. In general, a moisture-curable hot melt adhesive can be made to have a high molecular weight by a chemical reaction and can exhibit adhesiveness and the like. A urethane prepolymer having an isocyanate group at the end of the polymerization chain can react with moisture to cure (form a cured product), and thus the urethane prepolymer alone can function as a moisture-curable hot melt adhesive. In addition, the moisture-curable hot melt adhesive may contain components other than the urethane prepolymer.
［ウレタンプレポリマー］
　ウレタンプレポリマーは、ポリブタジエンポリオール及び水素化ポリブタジエンポリオールからなる群より選ばれる少なくとも１種に由来する構造単位並びにポリイソシアネートに由来する構造単位を含む重合鎖と、重合鎖の末端にイソシアネート基と、を有する。ウレタンプレポリマーは、通常、ポリブタジエンポリオール及び水素化ポリブタジエンポリオールからなる群より選ばれる少なくとも１種に、ポリイソシアネートを反応させて得ることができる。すなわち、ウレタンプレポリマーは、このようなポリオールとポリイソシアネートとの反応物であってよい。 [Urethane Prepolymer]
The urethane prepolymer has a polymer chain containing a structural unit derived from at least one selected from the group consisting of polybutadiene polyol and hydrogenated polybutadiene polyol and a polyisocyanate derived structure, and an isocyanate group at the end of the polymer chain Have. The urethane prepolymer can be generally obtained by reacting polyisocyanate with at least one selected from the group consisting of polybutadiene polyol and hydrogenated polybutadiene polyol. That is, the urethane prepolymer may be a reactant of such a polyol and a polyisocyanate.
（ポリブタジエンポリオール及び水素化ポリブタジエンポリオール）
　ポリブタジエンポリオールは、ブタジエンに由来する重合鎖とその重合鎖の両末端等に水酸基とを有する化合物であり、水素化ポリブタジエンポリオールは、ポリブタジエンポリオールの水素添加物である。ポリブタジエンポリオール及び水素化ポリブタジエンポリオールは、分子内に平均１．８～２．５程度の水酸基を有していてよい。ポリブタジエン及びその水素添加物に由来する重合鎖は、エラストマとして作用し得るものであり、このような重合鎖を有することによって、ウレタンプレポリマーに接着性及び伸縮性を付与することが可能となる。ウレタンプレポリマーの重合鎖は、水素化ポリブタジエンポリオールに由来する構造単位を含むことが好ましい。 (Polybutadiene polyol and hydrogenated polybutadiene polyol)
The polybutadiene polyol is a compound having a polymer chain derived from butadiene and hydroxyl groups at both ends of the polymer chain, etc. The hydrogenated polybutadiene polyol is a hydrogenated product of polybutadiene polyol. The polybutadiene polyol and the hydrogenated polybutadiene polyol may have an average of about 1.8 to 2.5 hydroxyl groups in the molecule. Polybutadiene and a polymer chain derived from its hydrogenated substance can act as an elastomer, and having such a polymer chain makes it possible to impart adhesiveness and elasticity to the urethane prepolymer. The polymerization chain of the urethane prepolymer preferably contains structural units derived from a hydrogenated polybutadiene polyol.
　ポリブタジエンポリオール及び水素化ポリブタジエンポリオールは市販品をそのまま用いることができる。水素化ポリブタジエンポリオールの市販品としては、例えば、ＧＩ－１０００、ＧＩ－２０００、ＧＩ－３０００（いずれも商品名、日本槽達株式会社製）等が挙げられる。ポリブタジエンポリオールの市販品としては、例えば、Ｇ－１０００、Ｇ－２０００、Ｇ－３０００（いずれも商品名、日本槽達株式会社製）、Ｐｏｌｙ　ｂｄ　Ｒ－１５ＨＴ、Ｐｏｌｙ　ｂｄ　Ｒ－４５ＨＴ（いずれも商品名、出光興産株式会社製）、Ｋｒａｓｏｌ　ＬＢＨ－Ｐ３０００（商品名、クレイバレー社製）等が挙げられる。これらは、１種を単独で用いてもよく、２種以上を併用して用いてもよい。 As the polybutadiene polyol and hydrogenated polybutadiene polyol, commercially available products can be used as they are. Examples of commercially available products of hydrogenated polybutadiene polyol include GI-1000, GI-2000, GI-3000 (all trade names, manufactured by Nippon Tanka Co., Ltd.) and the like. As a commercial item of polybutadiene polyol, for example, G-1000, G-2000, G-3000 (all are trade names, manufactured by Nippon Tanka Co., Ltd.), Poly bd R-15HT, Poly bd R-45 HT (all are goods) Names, manufactured by Idemitsu Kosan Co., Ltd., Krasol LBH-P3000 (trade name, manufactured by Clay Valley, Inc.), and the like. One of these may be used alone, or two or more may be used in combination.
　ポリブタジエンポリオール及び水素化ポリブタジエンポリオールの数平均分子量（Ｍｎ）は、粘度及び接着力のバランスの観点から、５００～１０００００、７００～５００００、又は９００～１００００であってよい。本明細書において、数平均分子量（Ｍｎ）は、ゲルパーミエーションクロマトグラフィー（ＧＰＣ）により測定され、標準ポリスチレン換算した値である。 The number average molecular weight (Mn) of the polybutadiene polyol and the hydrogenated polybutadiene polyol may be 500 to 100,000, 700 to 50,000, or 900 to 10,000, from the viewpoint of the balance of viscosity and adhesion. In the present specification, the number average molecular weight (Mn) is a value measured by gel permeation chromatography (GPC) and converted into standard polystyrene.
　ウレタンプレポリマーの調製においては、ポリブタジエンポリオール及び水素化ポリブタジエンポリオールとともにポリイソシアネートと反応可能なポリオール（以下、「その他のポリオール」という。）を併用してもよい。その他のポリオールとしては、例えば、ポリエステルポリオール、ポリエーテルポリオール、ポリアクリレートポリオール、ポリカーボネーポリオール、ポリシロキサンポリオール、ポリイソプレンポリオール、ポリオレフィンポリオール等が挙げられる。その他のポリオールは、１種を単独で用いてもよく、２種以上を併用して用いてもよい。 In the preparation of the urethane prepolymer, a polybutadiene polyol and a hydrogenated polybutadiene polyol may be used in combination with a polyol capable of reacting with a polyisocyanate (hereinafter referred to as "other polyol"). Examples of other polyols include polyester polyols, polyether polyols, polyacrylate polyols, polycarbonate polyols, polysiloxane polyols, polyisoprene polyols, polyolefin polyols and the like. The other polyols may be used alone or in combination of two or more.
　ポリブタジエンポリオール及び水素化ポリブタジエンポリオールの合計の含有量は、伸縮性の観点から、ポリオール全量（ポリブタジエンポリオール及び水素化ポリブタジエンポリオール、並びにその他のポリオール）を基準として、３０質量％以上であってよい。ポリブタジエンポリオール及び水素化ポリブタジエンポリオールの含有量は、ポリオール全量を基準として、４０質量％以上、５０質量％以上、７０質量％以上、又は９０質量％以上であってよい。ポリオールは、ポリブタジエンポリオール及び水素化ポリブタジエンポリオールのみから構成されるものであってよい。ポリブタジエンジオール及び水素化ポリブタジエンジオールの含有量が多くなるほど、湿気硬化型ホットメルト接着剤の硬化後の伸縮回復率が高くなる傾向にある。 From the viewpoint of stretchability, the total content of the polybutadiene polyol and the hydrogenated polybutadiene polyol may be 30% by mass or more based on the total amount of the polyols (polybutadiene polyol and hydrogenated polybutadiene polyol, and other polyols). The content of the polybutadiene polyol and the hydrogenated polybutadiene polyol may be 40% by mass, 50% by mass or more, 70% by mass or more, or 90% by mass or more, based on the total amount of the polyol. The polyol may be composed only of polybutadiene polyol and hydrogenated polybutadiene polyol. As the content of the polybutadiene diol and the hydrogenated polybutadiene diol increases, the stretch recovery after curing of the moisture-curable hot melt adhesive tends to increase.
　その他のポリオールの含有量は、ポリオール全量を基準として、０～７０質量％、０～６０質量％、０～５０質量％、０～３０質量％、又は０～１０質量％であってよい。 The content of the other polyol may be 0 to 70% by mass, 0 to 60% by mass, 0 to 50% by mass, 0 to 30% by mass, or 0 to 10% by mass, based on the total amount of the polyol.
（ポリイソシアネート）
　ポリイソシアネートは、イソシアネート基を２個以上有するポリイソシアネートであれば特に制限なく用いることができる。ポリイソシアネートは、反応時の取り扱い性の観点から、ジイソシアネートであることが好ましい。このようなジイソシアネートとしては、例えば、ジフェニルメタンジイソシアネート、ジメチルジフェニルメタンジイソシアネート、トリレンジイソシアネート、キシリレンジイソシアネート、ｐ－フェニレンジイソシアネート等の芳香族ポリイソシアネート、ヘキサメチレンジイソシアネート等の脂肪族ポリイソシアネート、ジシクロヘキシルメタンジイソシアネート、イソフォロンジイソシアネート等の脂環式ポリイソシアネート等が挙げられる。ポリイソシアネートは、１種を単独で用いてもよく、２種以上を併用して用いてもよい。これらのうち、ポリイソシアネートは、ジフェニルメタンジイソシアネートを含むことが好ましい。 (Polyisocyanate)
The polyisocyanate is not particularly limited as long as it is a polyisocyanate having two or more isocyanate groups. The polyisocyanate is preferably a diisocyanate from the viewpoint of handleability at the time of reaction. Examples of such diisocyanates include aromatic polyisocyanates such as diphenylmethane diisocyanate, dimethyl diphenylmethane diisocyanate, tolylene diisocyanate, xylylene diisocyanate, p-phenylene diisocyanate, aliphatic polyisocyanates such as hexamethylene diisocyanate, dicyclohexylmethane diisocyanate, iso Alicyclic polyisocyanates such as folone diisocyanate may, for example, be mentioned. The polyisocyanate may be used alone or in combination of two or more. Among these, the polyisocyanate preferably contains diphenylmethane diisocyanate.
　ウレタンプレポリマーは、ポリオールに由来する構造単位及びポリイソシアネートに由来する構造単位を含む重合鎖の末端にイソシアネート基を有する。このようなウレタンプレポリマーを合成する場合、ポリイソシアネートとポリオールとの混合割合は、ポリイソシアネートのイソシアネート基（ＮＣＯ）当量／ポリオールの水酸基（ＯＨ）当量（（ＮＣＯ）当量／（ＯＨ）当量）を１．１以上に調整することが好ましい。（ＮＣＯ）当量／（ＯＨ）当量は、１．１～２．２又は１．１～２．１であってもよい。（ＮＣＯ）当量／（ＯＨ）当量が１．１以上であると、得られるウレタンプレポリマーの粘度の上昇を抑えることができ、作業性が向上し易くなる傾向にある。（ＮＣＯ）当量／（ＯＨ）当量が２．２以下であると、ウレタンプレポリマーの湿気硬化反応の際の発泡が生じ難くなり、接着性の低下を抑制し易くなる傾向にある。 The urethane prepolymer has an isocyanate group at the end of a polymer chain containing a structural unit derived from a polyol and a structural unit derived from a polyisocyanate. When such a urethane prepolymer is synthesized, the mixing ratio of polyisocyanate and polyol is: isocyanate group (NCO) equivalent of polyisocyanate / hydroxyl group equivalent (OH) of polyol ((NCO) equivalent / (OH) equivalent) It is preferable to adjust to 1.1 or more. The (NCO) equivalent / (OH) equivalent may be 1.1 to 2.2 or 1.1 to 2.1. When the (NCO) equivalent / (OH) equivalent is 1.1 or more, the increase in the viscosity of the resulting urethane prepolymer can be suppressed, and the workability tends to be easily improved. When the (NCO) equivalent / (OH) equivalent is 2.2 or less, foaming during the moisture curing reaction of the urethane prepolymer is less likely to occur, and the decrease in adhesion tends to be suppressed.
　ウレタンプレポリマーの重量平均分子量（Ｍｗ）は、１００００以上、１２０００以上、又は１４０００以上であってよく、１００００００以下、５０００００以下、３０００００以下、２０００００以下、又は１５００００以下であってよい。ウレタンプレポリマーの重量平均分子量（Ｍｗ）は、１００００～１００００００、５００００～５０００００、又は１０００００～３０００００であってよい。ウレタンプレポリマーの重量平均分子量は、一般に（ＮＣＯ）当量／（ＯＨ）当量を１に近づけるほど、高くできる傾向にある。また、ウレタンプレポリマーの重量平均分子量が高くなるほど、高粘度になる傾向にある。 The weight average molecular weight (Mw) of the urethane prepolymer may be 10000 or more, 12000 or more, or 14000 or more, and may be 1000000 or less, 500000 or less, 300000 or less, 200,000 or less, or 150,000 or less. The weight average molecular weight (Mw) of the urethane prepolymer may be 10,000 to 1,000,000, 50,000 to 500,000, or 100,000 to 300,000. Generally, the weight average molecular weight of the urethane prepolymer tends to be higher as the (NCO) equivalent / (OH) equivalent is closer to 1. In addition, the higher the weight average molecular weight of the urethane prepolymer, the higher the viscosity tends to be.
　湿気硬化型ホットメルト接着剤は、ゴム弾性を高め、より強固な接着性を付与する観点から、熱可塑性ポリマーをさらに含有していてもよい。熱可塑性ポリマーとしては、例えば、ポリウレタン、エチレン系共重合体、プロピレン系共重合体、塩化ビニル系共重合体、アクリル共重合体、スチレン－共役ジエンブロック共重合体等が挙げられる。熱可塑性ポリマーの含有量は、湿気硬化型ホットメルト接着剤の全量を基準として、１０～５０質量％であってよい。 The moisture-curable hot melt adhesive may further contain a thermoplastic polymer from the viewpoint of enhancing the rubber elasticity and imparting stronger adhesion. Examples of the thermoplastic polymer include polyurethane, ethylene-based copolymer, propylene-based copolymer, vinyl chloride-based copolymer, acrylic copolymer, and styrene-conjugated diene block copolymer. The content of the thermoplastic polymer may be 10 to 50% by mass based on the total amount of the moisture curable hot melt adhesive.
　湿気硬化型ホットメルト接着剤は、より強固な接着性を付与する観点から、粘着付与剤をさらに含有していてもよい。粘着付与剤としては、例えば、ロジン樹脂、ロジンエステル樹脂、水添ロジンエステル樹脂、テルペン樹脂、テルペンフェノール樹脂、水添テルペン樹脂、石油樹脂、水添石油樹脂、クマロン樹脂、ケトン樹脂、スチレン樹脂、変性スチレン樹脂、キシレン樹脂、エポキシ樹脂等が挙げられる。粘着付与剤の含有量は、湿気硬化型ホットメルト接着剤の全量を基準として、１０～５０質量％であってよい。また、熱可塑性ポリマー及び粘着付与剤の合計の含有量は、湿気硬化型ホットメルト接着剤の全量を基準として、１０～５０質量％であってもよい。 The moisture-curable hot melt adhesive may further contain a tackifier from the viewpoint of imparting stronger adhesiveness. As a tackifier, for example, rosin resin, rosin ester resin, hydrogenated rosin ester resin, terpene resin, terpene phenol resin, hydrogenated terpene resin, petroleum resin, hydrogenated petroleum resin, coumarone resin, ketone resin, styrene resin, Modified styrene resin, xylene resin, epoxy resin and the like can be mentioned. The content of the tackifier may be 10 to 50% by mass based on the total amount of the moisture-curable hot melt adhesive. In addition, the total content of the thermoplastic polymer and the tackifier may be 10 to 50% by mass based on the total amount of the moisture-curable hot melt adhesive.
　湿気硬化型ホットメルト接着剤は、触媒をさらに含有していてもよい。触媒としては、例えば、ジブチルスズジラウレート、ジブチルスズオクテート、ジメチルシクロヘキシルアミン、ジメチルベンジルアミン、トリオクチルアミン、ジモルホリノジエチルエーテル等が挙げられる。触媒の含有量は、湿気硬化型ホットメルト接着剤の全量を基準として、０．００１～０．５質量％であってよい。 The moisture curable hot melt adhesive may further contain a catalyst. Examples of the catalyst include dibutyltin dilaurate, dibutyltin octoate, dimethylcyclohexylamine, dimethylbenzylamine, trioctylamine, dimorpholinodiethyl ether and the like. The content of the catalyst may be 0.001 to 0.5% by mass based on the total amount of the moisture curing type hot melt adhesive.
　湿気硬化型ホットメルト接着剤は、必要に応じて、その他の成分をさらに含有していてもよい。その他の成分としては、例えば、酸化防止剤、顔料、紫外線吸収剤、界面活性剤、難燃剤、充填剤、光発色剤、熱発色防止剤、香料、イメージング剤、熱架橋剤等が挙げられる。その他の成分の含有量は、湿気硬化型ホットメルト接着剤の全量を基準として、０．００１～１０質量％であってよい。 The moisture-curable hot melt adhesive may further contain other components, as required. Other components include, for example, antioxidants, pigments, UV absorbers, surfactants, flame retardants, fillers, photochromic agents, thermal color development inhibitors, fragrances, imaging agents, thermal crosslinking agents, and the like. The content of the other components may be 0.001 to 10% by mass based on the total amount of the moisture-curable hot melt adhesive.
　湿気硬化型ホットメルト接着剤（硬化前の湿気硬化型ホットメルト接着剤）の１２０℃における粘度は、０．０１Ｐａ・ｓ以上、０．０５Ｐａ・ｓ以上、０．１Ｐａ・ｓ以上、又は０．５Ｐａ・ｓ以上であってよく、１００Ｐａ・ｓ以下、８０Ｐａ・ｓ以下、６０Ｐａ・ｓ以下、又は５０Ｐａ・ｓ以下であってよい。１２０℃における粘度が上記範囲内にあることで、ディスペンサー等で塗布する際の作業性が良好になる。 The viscosity at 120 ° C. of the moisture-curable hot melt adhesive (moisture-curable hot melt adhesive before curing) is 0.01 Pa · s or more, 0.05 Pa · s or more, 0.1 Pa · s or more, or 0. It may be 5 Pa · s or more, 100 Pa · s or less, 80 Pa · s or less, 60 Pa · s or less, or 50 Pa · s or less. When the viscosity at 120 ° C. is in the above range, the workability at the time of coating with a dispenser or the like is improved.
　湿気硬化型ホットメルト接着剤は、接着剤に含まれるウレタンプレポリマーの末端イソシアネート基が空気中の水分又は被着体表面の水分と反応することから、例えば、２３℃で１日間養生（放置）することによって、硬化させることが可能となる（湿気硬化型ホットメルト接着剤の硬化物を得ることが可能となる）。 The moisture-curable hot melt adhesive is, for example, cured for 1 day at 23 ° C. because the terminal isocyanate group of the urethane prepolymer contained in the adhesive reacts with the moisture in the air or the moisture on the surface of the adherend. It is possible to cure (make it possible to obtain a cured product of a moisture-curable hot melt adhesive).
　湿気硬化型ホットメルト接着剤を用いて被着体同士を圧着した後、接着剤が硬化する前に測定される接着強度（湿気硬化型ホットメルト接着剤の初期の接着強度）は、０．０１３Ｎ／ｍｍ（０．１Ｎ／８ｍｍ）以上、０．０３８Ｎ／ｍｍ（０．３Ｎ／８ｍｍ）以上、０．０６３Ｎ／ｍｍ（０．５Ｎ／８ｍｍ）以上、０．１２５Ｎ／ｍｍ（１．０Ｎ／８ｍｍ）以上、又は０．１８８Ｎ／ｍｍ（１．５Ｎ／８ｍｍ）以上であってよい。硬化物の接着強度の上限は、特に制限されないが、１．５Ｎ／ｍｍ（１２Ｎ／８ｍｍ）以下であってよい。なお、本明細書において、初期の接着強度は、実施例に記載の方法によって測定される値を意味する。すなわち、初期の接着強度は、湿気硬化型ホットメルト接着剤を用いて被着体同士を１２０℃で圧着することによって得られる圧着体において、圧着した時点から５分経過後の圧着体の湿気硬化型ホットメルト接着剤の接着強度を意味する。 The adhesive strength (the initial adhesive strength of the moisture-curable hot melt adhesive) measured before the adhesive is cured after pressure-adhering the adherends to each other using the moisture-curable hot melt adhesive is 0.013 N. / Mm (0.1 N / 8 mm) or more, 0.038 N / mm (0.3 N / 8 mm) or more, 0.063 N / mm (0.5 N / 8 mm) or more, 0.125 N / mm (1.0 N / 8 mm) Or higher, or 0.188 N / mm (1.5 N / 8 mm) or higher. The upper limit of the adhesive strength of the cured product is not particularly limited, but may be 1.5 N / mm (12 N / 8 mm) or less. In addition, in this specification, the adhesive strength of an initial stage means the value measured by the method as described in an Example. That is, in the pressure-bonded body obtained by pressure-adhering the adherends at 120 ° C. using a moisture curing type hot melt adhesive, the initial adhesive strength is moisture curing of the pressure-bonded body after 5 minutes from the time of pressure bonding. The adhesive strength of the mold hot melt adhesive is meant.
　湿気硬化型ホットメルト接着剤を用いて被着体同士を圧着した後、接着剤が硬化した後に測定される接着強度（湿気硬化型ホットメルト接着剤の硬化後の接着強度）は、０．０６３Ｎ／ｍｍ（０．５Ｎ／８ｍｍ）以上、０．１２５Ｎ／ｍｍ（１．０Ｎ／８ｍｍ）以上、０．１８８Ｎ／ｍｍ（１．５Ｎ／８ｍｍ）以上、０．３７５Ｎ／ｍｍ（３Ｎ／８ｍｍ）以上、０．６２５Ｎ／ｍｍ（５Ｎ／８ｍｍ）以上、又は０．８７５Ｎ／ｍｍ（７Ｎ／８ｍｍ）以上であってよい。硬化後の接着強度の上限は、特に制限されないが、２．５Ｎ／ｍｍ（２０Ｎ／８ｍｍ）以下であってよい。なお、本明細書において、硬化後の接着強度は、実施例に記載の方法によって測定される値を意味する。すなわち、硬化後の接着強度は、湿気硬化型ホットメルト接着剤を用いて被着体同士を１２０℃で圧着することによって得られる圧着体を、２３℃、５０％ＲＨの恒温槽で１日間養生し、得られる接着体の湿気硬化型ホットメルト接着剤の硬化後の接着強度を意味する。 The adhesive strength (adhesive strength after curing of the moisture-curable hot melt adhesive) measured after the adhesive is cured after the adherends are pressure-bonded to each other using the moisture-curable hot melt adhesive is 0.063 N / Mm (0.5 N / 8 mm) or more, 0.125 N / mm (1.0 N / 8 mm) or more, 0.188 N / mm (1.5 N / 8 mm) or more, 0.375 N / mm (3 N / 8 mm) or more , 0.625 N / mm (5 N / 8 mm) or more, or 0.875 N / mm (7 N / 8 mm) or more. The upper limit of the adhesive strength after curing is not particularly limited, but may be 2.5 N / mm (20 N / 8 mm) or less. In the present specification, the adhesive strength after curing means a value measured by the method described in the examples. That is, the adhesive strength after curing is that a pressure-bonded body obtained by pressure-adhering adherends at 120 ° C. using a moisture-curable hot melt adhesive is cured for 1 day in a thermostatic chamber at 23 ° C. and 50% RH. And the adhesive strength after curing of the moisture-curable hot melt adhesive of the resulting bonded body.
　湿気硬化型ホットメルト接着剤の硬化後の引張弾性率（湿気硬化型ホットメルト接着剤の硬化物の引張弾性率）は、１０ＭＰａ以下である。湿気硬化型ホットメルト接着剤の硬化後の引張弾性率は、柔軟性の観点から、０．０１ＭＰａ以上、０．０５ＭＰａ以上、又は０．１ＭＰａ以上であってよく、８ＭＰａ以下、６ＭＰａ以下、又は４ＭＰａ以下であってよい。衣服又はウェアラブル製品に使用する場合、引張弾性率が上記範囲内にあることで、装着した際の違和感をより少なくすることができる。なお、本明細書において、硬化後の引張弾性率は、実施例に記載の方法によって測定される値を意味する。すなわち、硬化後の引張弾性率は、湿気硬化型ホットメルト接着剤を、２３℃、５０％ＲＨの恒温槽で１日間養生することによって硬化させ、得られる硬化物の引張弾性率を意味する。 The tensile modulus after curing of the moisture-curable hot melt adhesive (the tensile modulus of the cured product of the moisture-curable hot melt adhesive) is 10 MPa or less. The tensile modulus after curing of the moisture-curable hot melt adhesive may be 0.01 MPa or more, 0.05 MPa or more, or 0.1 MPa or more from the viewpoint of flexibility, 8 MPa or less, 6 MPa or less, or 4 MPa It may be the following. When using for clothes or a wearable product, the sense of incongruity at the time of wearing can be lessened because tensile elastic modulus is in the above-mentioned range. In the present specification, the tensile modulus after curing means a value measured by the method described in the examples. That is, the tensile elastic modulus after curing means the tensile elastic modulus of a cured product obtained by curing a moisture curing type hot melt adhesive by curing for 1 day in a constant temperature bath at 23 ° C. and 50% RH.
　湿気硬化型ホットメルト接着剤の硬化後の伸縮回復率（湿気硬化型ホットメルト接着剤の硬化物の伸縮回復率）は、９０％以上、９３％以上、又は９５％以上であってよい。なお、本明細書において、硬化後の伸縮回復率は、実施例に記載の方法によって測定される値を意味する。すなわち、硬化後の伸縮回復率は、湿気硬化型ホットメルト接着剤を、２３℃、５０％ＲＨの恒温槽で１日間養生することによって硬化させ、得られる硬化物の伸縮回復率を意味する。 The stretch recovery after curing of the moisture-curable hot melt adhesive (stretch recovery of the cured product of the moisture-curable hot melt adhesive) may be 90% or more, 93% or more, or 95% or more. In addition, in this specification, the expansion-contraction recovery factor after hardening means the value measured by the method as described in an Example. That is, the stretch recovery rate after curing means the stretch recovery rate of a cured product obtained by curing a moisture curing type hot melt adhesive by curing it in a constant temperature bath at 23 ° C. and 50% RH for 1 day.
　湿気硬化型ホットメルト接着剤は、例えば、６０～１３０℃で溶融してから、被着体に塗布することによって使用することができる。塗布方法は、特に制限されないが、例えば、ダイコーター、ロールコーター、スプレー等の塗布装置を用いる方法が挙げられる。小型部品等の狭小な部位へ塗布する場合には、ディスペンサーが適している。 The moisture-curable hot melt adhesive can be used, for example, by melting it at 60 to 130 ° C. and then applying it to an adherend. The coating method is not particularly limited, and examples thereof include methods using a coating apparatus such as a die coater, a roll coater, or a spray. A dispenser is suitable for application to narrow parts such as small parts.
　被着体は、特に制限されないが、例えば、布又は紙であってよい。本実施形態に係る湿気硬化型ホットメルト接着剤は、複数の布又は紙を互いに貼り合わせるために好適に用いることができる。ここで、貼り合わせの対象（被着体）は、布と布、紙と紙、又は布と紙であってよい。 The adherend is not particularly limited, and may be, for example, cloth or paper. The moisture-curable hot melt adhesive according to the present embodiment can be suitably used to bond a plurality of cloths or papers together. Here, the target of bonding (adherend) may be cloth and cloth, paper and paper, or cloth and paper.
　湿気硬化型ホットメルト接着剤は、フィルム状に形成して用いてもよい。湿気硬化型ホットメルト接着剤フィルムは、例えば、湿気硬化型ホットメルト接着剤をＰＥＴフィルム等の支持フィルム上に塗布することによって形成することができる。湿気硬化型ホットメルト接着剤フィルムの厚さは、１０μｍ以上、２０μｍ以上、又は３０μｍ以上であってよく、３００μｍ以下、２５０μｍ以下、又は２００μｍ以下であってよい。湿気硬化型ホットメルト接着剤フィルムが厚くなると、接着性を担保することができ、湿気硬化型ホットメルト接着剤フィルムが薄くなると、伸縮性をより確保し易い傾向にある。 The moisture-curable hot melt adhesive may be used in the form of a film. The moisture curable hot melt adhesive film can be formed, for example, by applying a moisture curable hot melt adhesive on a support film such as a PET film. The thickness of the moisture curable hot melt adhesive film may be 10 μm or more, 20 μm or more, or 30 μm or more, and may be 300 μm or less, 250 μm or less, or 200 μm or less. When the moisture-curable hot melt adhesive film is thick, adhesiveness can be ensured, and when the moisture-curable hot melt adhesive film is thin, the stretchability tends to be more easily secured.
　湿気硬化型ホットメルト接着剤は、例えば、ポリブタジエンポリオール及び水素化ポリブタジエンポリオールからなる群より選ばれる少なくとも１種を含むポリオールとポリイソシアネートとを反応させて、ウレタンプレポリマーを得る工程と、必要に応じて、ウレタンプレポリマーとその他の任意成分を混合する工程と、を備える方法によって製造される。 The moisture-curable hot melt adhesive is obtained, for example, by reacting a polyol containing at least one member selected from the group consisting of polybutadiene polyol and hydrogenated polybutadiene polyol with a polyisocyanate to obtain a urethane prepolymer, if necessary And mixing the urethane prepolymer with other optional components.
　本実施形態に係る湿気硬化型ホットメルト接着剤は、衣服等のアパレル商品、サポーター、カバン、財布、インテリア、各種カバー、ケース、ウェアラブル機器などに好適に用いることができる。 The moisture curing type hot melt adhesive according to the present embodiment can be suitably used for apparel products such as clothes, supporters, bags, wallets, interiors, various covers, cases, wearable devices, and the like.
＜接着体＞
　一実施形態に係る接着体は、複数の布又は紙と、複数の布又は紙を互いに接着する上述の湿気硬化型ホットメルト接着剤の硬化物と、を備える。本実施形態に係る接着体は、例えば、被着体が布と布との接着体である場合、無縫製衣類等として利用することができる。 <Adhesive body>
An adhesive according to one embodiment comprises a plurality of cloths or papers, and a cured product of the above-mentioned moisture-curable hot melt adhesive for bonding a plurality of cloths or papers to one another. The adhesive body according to the present embodiment can be used as a non-sewn garment or the like, for example, when the adherend is an adhesive body of cloth and cloth.
　接着体は、例えば、布又は紙に、上述の湿気硬化型ホットメルト接着剤を塗布して接着剤層を形成し、接着剤層上にさらに布又は紙を配置して圧着して接着体前駆体を得る工程と、得られた接着体前駆体を空気中で養生（例えば、２３℃で１日間養生）し、接着剤層（湿気硬化型ホットメルト接着剤）を硬化させる工程と、を備える方法によって製造することができる。接着体前駆体を得る工程では、例えば、加圧ロール等を用いることができる。 The adhesive may be, for example, a cloth or paper coated with the above-mentioned moisture-curable hot melt adhesive to form an adhesive layer, and a cloth or paper placed on the adhesive layer and crimped to form an adhesive precursor. And curing the resulting adhesive precursor in air (eg, curing for 1 day at 23 ° C.) and curing the adhesive layer (moisture-curable hot melt adhesive). It can be manufactured by the method. In the step of obtaining an adhesive precursor, for example, a pressure roll or the like can be used.
　図１は、一実施形態に係る接着体を作製する工程の一例を示す模式図であり、図１（ａ）、（ｂ）、（ｃ）、及び（ｄ）は、各工程を示す模式図である。図１を参照して、布として伸縮性生地を用いた接着体の作製工程について説明する。 FIG. 1: is a schematic diagram which shows an example of the process of producing the adhesive body which concerns on one Embodiment, and FIG. 1 (a), (b), (c) and (d) is a schematic diagram which shows each process. It is. With reference to FIG. 1, the manufacturing process of the bonded body using elastic fabric as cloth is demonstrated.
　まず、伸縮性生地１を治具１０に沿わせるように設置する（図１の（ａ）参照）。次いで、本実施形態に係る湿気硬化型ホットメルト接着剤を伸縮性生地１の所定部分に塗布して、接着剤層４を形成する（図１の（ｂ）参照）。治具１０の材質及び形状は特に限定されず、目的に応じて適宜選択することができる。接着剤の塗布は、例えば、ディスペンサーを用いて行ってもよい。次に、伸縮性生地２を接着剤層４上に配置して、伸縮性生地２の上からロール等により圧力をかけながら、伸縮性生地１と伸縮性生地２とを接着剤層４を介して貼り合わせて、接着体前駆体を得る（図１の（ｃ）及び（ｄ）参照）。その後、接着体前駆体を養生することによって接着剤層４が湿気硬化して、伸縮性生地の接着体を得ることができる。 First, the stretchable fabric 1 is installed along the jig 10 (see (a) of FIG. 1). Next, the moisture-curable hot melt adhesive according to the present embodiment is applied to a predetermined portion of the stretchable fabric 1 to form an adhesive layer 4 (see (b) in FIG. 1). The material and shape of the jig 10 are not particularly limited, and can be appropriately selected according to the purpose. The application of the adhesive may be performed, for example, using a dispenser. Next, the stretchable fabric 2 is placed on the adhesive layer 4 and the stretchable fabric 1 and the stretchable fabric 2 are interposed between the adhesive layer 4 while applying pressure from above the stretchable fabric 2 by a roll or the like. It bonds together and obtains an adhesion body precursor (refer (c) and (d) of FIG. 1). Thereafter, by curing the adhesive precursor, the adhesive layer 4 is moisture-cured to obtain an adhesive of the stretchable fabric.
　図１の（ｂ）において、離型性基材上に予め形成しておいた接着剤を伸縮性生地１上に転写して、接着剤層４を形成してもよい。また、接着剤を伸縮性生地２に設けて、伸縮性生地１と貼り合わせてもよい。 In (b) of FIG. 1, the adhesive previously formed on the releasable substrate may be transferred onto the stretchable fabric 1 to form the adhesive layer 4. Alternatively, an adhesive may be provided on the stretchable fabric 2 to be bonded to the stretchable fabric 1.
　以下、本発明について実施例を挙げてより具体的に説明する。ただし、本発明はこれら実施例に限定されるものではない。 Hereinafter, the present invention will be more specifically described by way of examples. However, the present invention is not limited to these examples.
（実施例１～６）
＜ウレタンプレポリマー（湿気硬化型ホットメルト接着剤）の合成＞
　表１に示す種類及び質量部のポリオール（ポリブタジエンポリオール又は水素化ポリブタジエンポリオール）及びポリイソシアネートを用いた。予め真空乾燥機によって脱水処理したポリオールに、ポリイソシアネートとしてジフェニルメタンジイソシアネートを、ポリイソシアネートのイソシアネート基のポリオールの水酸基に対するモル比（（ＮＣＯ）当量／（ＯＨ）当量）が表１で示す数値となるように加えて、均一になるまで混合した。次いで、得られた混合物を１１０℃で１時間反応させ、更に１１０℃で１時間減圧脱泡撹拌し、ウレタンプレポリマーを調製した。表１に示すとおり、（ＮＣＯ）当量／（ＯＨ）当量が１より大きいことから、得られるウレタンプレポリマーは、ポリブタジエンポリオール及び水素化ポリブタジエンポリオールからなる群より選ばれる少なくとも１種に由来する構造単位並びにポリイソシアネートに由来する構造単位を含む重合鎖とその重合鎖の末端にイソシアネート基とを有することが推測される。得られたウレタンプレポリマーは、そのまま湿気硬化型ホットメルト接着剤として用いた。 (Examples 1 to 6)
<Synthesis of urethane prepolymer (moisture curing type hot melt adhesive)>
Polyols (polybutadiene polyol or hydrogenated polybutadiene polyol) and polyisocyanates of the types and parts by weight shown in Table 1 were used. The molar ratio ((NCO) equivalent / (OH) equivalent) of the isocyanate group of the polyisocyanate to the hydroxyl group of the polyisocyanate of the polyisocyanate is as shown in Table 1 to the polyol previously dehydrated by a vacuum drier as polyisocyanate. And mixed until uniform. Then, the obtained mixture was reacted at 110 ° C. for 1 hour, and further degassed under reduced pressure at 110 ° C. for 1 hour to prepare a urethane prepolymer. As shown in Table 1, since the (NCO) equivalent / (OH) equivalent is greater than 1, the resulting urethane prepolymer is a structural unit derived from at least one selected from the group consisting of polybutadiene polyol and hydrogenated polybutadiene polyol. It is also presumed that the polymer has a polymer chain containing a structural unit derived from a polyisocyanate and an isocyanate group at the end of the polymer chain. The obtained urethane prepolymer was used as it was as a moisture-curable hot melt adhesive.
　表１に示す各成分の詳細は以下のとおりである。 The details of each component shown in Table 1 are as follows.
　水素化ポリブタジエンポリオールＡ－１：日本曹達株式会社製、商品名：ＧＩ－３０００、数平均分子量：３１００
　水素化ポリブタジエンポリオールＡ－２：日本曹達株式会社製、商品名：ＧＩ－１０００、数平均分子量：１５００
　ポリブタジエンポリオールＢ－１：出光興産株式会社製、商品名：Ｐｏｌｙ　ｂｄＴＭ　Ｒ－４５ＨＴ、数平均分子量：２８００
　ポリブタジエンポリオールＢ－２：クレイバレー社製、商品名：Ｋｒａｓｏｌ（登録商標）ＬＢＨ－Ｐ３０００、数平均分子量：３２００
　ジフェニルメタンジイソシアネート：日本ポリウレタン工業株式会社製、商品名：ミリオネートＭＴ Hydrogenated polybutadiene polyol A-1: Nippon Soda Co., Ltd., trade name: GI-3000, number average molecular weight: 3100
Hydrogenated polybutadiene polyol A-2: Nippon Soda Co., Ltd., trade name: GI-1000, number average molecular weight: 1,500
Polybutadiene polyol B-1: Idemitsu Kosan Co., Ltd., trade name: Poly bd TM R-45HT, a number average molecular weight: 2800
Polybutadiene polyol B-2: manufactured by Clay Valley, trade name: Krasol (registered trademark) LBH-P 3000, number average molecular weight: 3200
Diphenylmethane diisocyanate: manufactured by Nippon Polyurethane Industry Co., Ltd., trade name: Millionate MT
＜ウレタンプレポリマーの重量平均分子量＞
　得られたウレタンプレポリマーの重量平均分子量を、ゲルパーミエーションクロマトグラフィー（ＧＰＣ）法によって測定し、標準ポリスチレン検量線を用いて換算することによって求めた。測定装置として、ＨＬＣ－８２２０ＧＰＣ（東ソー株式会社製）を用い、溶離液として、テトラヒドロフランを用いた。結果を表１に示す。 <Weight average molecular weight of urethane prepolymer>
The weight average molecular weight of the obtained urethane prepolymer was measured by gel permeation chromatography (GPC) and determined by conversion using a standard polystyrene calibration curve. As a measuring device, HLC-8220GPC (manufactured by Tosoh Corp.) was used, and as an eluent, tetrahydrofuran was used. The results are shown in Table 1.
＜湿気硬化型ホットメルト接着剤の粘度＞
　硬化前の湿気硬化型ホットメルト接着剤の粘度を、レオメーター（ＡｎｔｏｎＰａａｒ社製、商品名：ＭＣＲ－３０１）を用い、周波数１Ｈｚ、歪振り角２％、ギャップ０．２ｍｍ、１２０℃の条件で測定した。結果を表１に示す。 <Viscosity of moisture curing type hot melt adhesive>
Using a rheometer (manufactured by Anton Paar, trade name: MCR-301), the viscosity of a moisture-curable hot melt adhesive before curing is set at a frequency of 1 Hz, a distortion swing angle of 2%, a gap of 0.2 mm, and 120 ° C. It was measured. The results are shown in Table 1.
＜湿気硬化型ホットメルト接着剤の硬化後の引張弾性率及び伸縮回復率＞
　実施例１～６の湿気硬化型ホットメルト接着剤を１２０℃で溶融してＰＥＴフィルム上に塗布し、バーコーターを用いて８０μｍの厚さに塗工することによって接着剤層を形成した。形成した接着剤層を２３℃、５０％ＲＨの恒温槽で１日間養生することによって硬化させ、接着剤層の硬化物を得た。得られた接着剤層の硬化物を５ｍｍ×５０ｍｍのサイズに打ち抜き、ＰＥＴフィルムを剥離して、測定試料とした。引張弾性率及び伸縮回復率は、引張試験機（株式会社島津製作所製、ＥＺ－Ｔｅｓｔ　ＥＺ－ＳＸ）を用いて、測定温度が２５℃、引張速度が１００ｍｍ／分、チャック間距離が３０ｍｍの条件で測定した。硬化後の引張弾性率は、引張初期段階の応力－歪み曲線の傾きから求めた。硬化後の伸縮回復率は、以下の方法によって求めた。測定試料を引張速度１００ｍｍ／分で１００％まで伸長させ、その後応力を解放した。１００％まで伸長させたときの歪み及び応力を解放してから１分後の歪みを測定し、それぞれＬ１及びＬ２とした。測定したＬ１及びＬ２を以下の式に代入することによって算出した。結果を表１に示す。
　伸縮回復率（％）＝（Ｌ１－Ｌ２）／Ｌ１×１００ <Tensile modulus and stretch recovery after curing of moisture-curable hot melt adhesive>
The moisture-curable hot melt adhesive of Examples 1-6 was melted at 120 ° C., applied onto a PET film, and applied to a thickness of 80 μm using a bar coater to form an adhesive layer. The formed adhesive layer was cured by curing in a thermostat bath at 23 ° C. and 50% RH for 1 day to obtain a cured product of the adhesive layer. The cured product of the adhesive layer obtained was punched into a size of 5 mm × 50 mm, and the PET film was peeled off to obtain a measurement sample. Tensile modulus and stretch recovery rate are measured using a tensile tester (EZ-Test EZ-SX, manufactured by Shimadzu Corporation) at a temperature of 25 ° C, a tensile speed of 100 mm / min, and a distance between chucks of 30 mm. It measured by. The tensile modulus after curing was determined from the slope of the stress-strain curve at the initial stage of tension. The elastic recovery after curing was determined by the following method. The measurement sample was stretched to 100% at a tensile speed of 100 mm / min and then the stress was released. The strain and stress when released to 100% were measured, and the strain one minute after release was measured, which were designated as L1 and L2, respectively. It calculated by substituting L1 and L2 which were measured to the following formula. The results are shown in Table 1.
Stretch recovery rate (%) = (L1-L2) / L1 x 100
＜湿気硬化型ホットメルト接着剤の接着強度＞
　実施例１～６の湿気硬化型ホットメルト接着剤を１２０℃で溶融して伸縮性布地（スパンデックス、東レ・オプロンテックス株式会社製、ライクラ（登録商標））上に塗布し、バーコーターにより８０μｍの厚さに塗工することによって接着剤層を形成した。形成した接着剤層上に、同じ伸縮性布地を配置し、１２０℃で圧着することによって圧着体を得た。圧着した時点から５分経過後の圧着体の接着強度を、フォースゲージ（株式会社イマダ製、ＤＳ２５０Ｎ）を用いて測定し、湿気硬化型ホットメルト接着剤の初期の接着強度を求めた。次いで、上記圧着体を２３℃、５０％ＲＨの恒温槽で１日間養生し、接着剤層を硬化させることによって接着体を作製した。接着体の接着強度を、引張試験機（株式会社島津製作所製、ＥＺ－Ｔｅｓｔ　ＥＺ－ＳＸ）を用いて、測定温度が２５℃、引張速度が１００ｍｍ／分の条件でＴ型剥離強度試験によって測定し、湿気硬化型ホットメルト接着剤の硬化後の接着強度を求めた。結果を表１に示す。 <Adhesive strength of moisture curing type hot melt adhesive>
The moisture-curable hot melt adhesive of Examples 1 to 6 is melted at 120 ° C. and applied onto a stretchable fabric (Spandex, Lycra (registered trademark) manufactured by Toray Oplontex Co., Ltd.), and 80 μm by a bar coater. An adhesive layer was formed by coating to a thickness of The same stretchable fabric was placed on the formed adhesive layer, and a crimped body was obtained by crimping at 120 ° C. The adhesive strength of the pressure-bonded body after 5 minutes from the time of pressure bonding was measured using a force gauge (manufactured by Imada Co., Ltd., DS250N) to determine the initial adhesive strength of the moisture-curable hot melt adhesive. Next, the above-mentioned pressure-bonded body was aged in a thermostat bath at 23 ° C. and 50% RH for 1 day, and the adhesive layer was cured to prepare an adhesive body. The adhesive strength of the adhesive is measured by a T-peel strength test under the conditions of a measurement temperature of 25 ° C. and a tensile speed of 100 mm / min using a tensile tester (EZ-Test EZ-SX manufactured by Shimadzu Corporation) The adhesive strength after curing of the moisture-curable hot melt adhesive was determined. The results are shown in Table 1.
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000001
　表１に示すとおり、実施例１～６の湿気硬化型ホットメルト接着剤は伸縮回復率が高く、布に適用した場合においても接着強度に優れていた。これらの結果より、本発明の湿気硬化型ホットメルト接着剤が、伸縮性に優れ、さらに布に適用した場合においても、接着性に優れることが確認された。 As shown in Table 1, the moisture-curable hot melt adhesives of Examples 1 to 6 had a high stretch recovery rate and were excellent in adhesive strength even when applied to a cloth. From these results, it was confirmed that the moisture-curable hot melt adhesive of the present invention is excellent in stretchability and also excellent in adhesiveness even when applied to a cloth.
　１，２…伸縮性生地、４…接着剤層、１０…治具。 1, 2 ... stretchable fabric, 4 ... adhesive layer, 10 ... jig.

Claims (5)

  1. 　ポリブタジエンポリオール及び水素化ポリブタジエンポリオールからなる群より選ばれる少なくとも１種に由来する構造単位並びにポリイソシアネートに由来する構造単位を含む重合鎖と、前記重合鎖の末端にイソシアネート基と、を有するウレタンプレポリマーを含有し、
    　硬化後の引張弾性率が１０ＭＰａ以下である、湿気硬化型ホットメルト接着剤。     Urethane prepolymer having a polymer chain including a structural unit derived from at least one selected from the group consisting of polybutadiene polyol and hydrogenated polybutadiene polyol and a polyisocyanate derived structure, and an isocyanate group at the end of the polymer chain Contains
    A moisture curable hot melt adhesive having a tensile modulus of 10 MPa or less after curing.
  2. 　硬化後の伸縮回復率が９０％以上である、請求項１に記載の湿気硬化型ホットメルト接着剤。 The moisture-curable hot melt adhesive according to claim 1, wherein the stretch recovery after curing is 90% or more.
  3. 　前記重合鎖が、水素化ポリブタジエンポリオールに由来する構造単位を含む、請求項１又は２に記載の湿気硬化型ホットメルト接着剤。 The moisture-curable hot melt adhesive according to claim 1, wherein the polymer chain contains a structural unit derived from a hydrogenated polybutadiene polyol.
  4. 　複数の布又は紙を互いに貼り合わせるために用いられる、請求項１～３のいずれか一項に記載の湿気硬化型ホットメルト接着剤。 The moisture curable hot melt adhesive according to any one of claims 1 to 3, which is used to bond a plurality of cloths or papers together.
  5. 　複数の布又は紙と、
    　前記複数の布又は紙を互いに接着する請求項１～４のいずれか一項に記載の湿気硬化型ホットメルト接着剤の硬化物と、
    を備える、接着体。     With multiple cloths or papers,
    The cured product of the moisture-curable hot melt adhesive according to any one of claims 1 to 4, wherein the plurality of cloths or papers are adhered to each other.
    , An adhesive body.
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JP2020069686A (en) * 2018-10-30 2020-05-07 株式会社ケー・エス・ティー Moisture-permeable waterproof sheet and method for producing the same
EP4103656A4 (en) * 2020-02-13 2023-09-27 Henkel AG & Co. KGaA Reactive hot melt adhesive composition and use thereof

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JP2020069686A (en) * 2018-10-30 2020-05-07 株式会社ケー・エス・ティー Moisture-permeable waterproof sheet and method for producing the same
EP4103656A4 (en) * 2020-02-13 2023-09-27 Henkel AG & Co. KGaA Reactive hot melt adhesive composition and use thereof

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